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Creators/Authors contains: "Dravid, Vinayak_P"

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  1. Abstract Electrochemical CO2reduction reaction (CO2‐RR) in non‐aqueous electrolytes offers significant advantages over aqueous systems, as it boosts CO2solubility and limits the formation of HCO3and CO32−anions. Metal–organic frameworks (MOFs) in non‐aqueous CO2‐RR makes an attractive system for CO2capture and conversion. However, the predominantly organic composition of MOFs limits their electrical conductivity and stability in electrocatalysis, where they suffer from electrolytic decomposition. In this work, electrically conductive and stable Zirconium (Zr)‐based porphyrin MOF, specifically PCN‐222, metalated with a single‐atom Cu has been explored, which serves as an efficient single‐atom catalyst (SAC) for CO2‐RR. PCN‐ 222(Cu) demonstrates a substantial enhancement in redox activity due to the synergistic effect of the Zr matrix and the single‐atom Cu site, facilitating complete reduction of C2species under non‐aqueous electrolytic conditions. The current densities achieved (≈100 mA cm2) are 4–5 times higher than previously reported values for MOFs, with a faradaic efficiency of up to 40% for acetate production, along with other multivariate C2products, which have never been achieved previously in non‐aqueous systems. Characterization using X‐ray and various spectroscopic techniques, reveals critical insights into the role of the Zr matrix and Cu sites in CO2reduction, benchmarking PCN‐222(Cu) for MOF‐based SAC electrocatalysis. 
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  2. Abstract Low‐symmetry van der Waals materials are promising candidates for the next generation of polarization‐sensitive on‐chip photonics since they do not require lattice matching for growth and integration. Due to their low‐symmetry crystal behavior, such materials exhibit anisotropic and polarization‐dependent optical properties for a wide range of optical frequencies. Here, depolarization characteristics of orthorhombic α‐MoO3is studied in the visible range. Using polarizers and analyzers, it is demonstrated that α‐MoO3has negligible loss and that birefringence values as high as 0.15 and 0.12 at 532 nm and 633 nm, respectively, are achievable. With such a high birefringence, quarter‐ and half‐wave plate actions are demonstrated for a 1400 nm α‐MoO3flake at green (532 nm) and red (633 nm) wavelengths, and polarizability as high as 90% is reported. Furthermore, a system of double α‐MoO3heterostructure layer is investigated that provides the possibility of tuning polarization as a function of rotation angle between the α‐MoO3layers. These findings pave the way to the promising future of on‐chip photonic heterostructures and twist‐optics that can dictate the polarization state of light. 
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